JPH08193129A - Polyamide-ester, its production and resin composition containing it - Google Patents

Abstract

PURPOSE: To obtain a polymer which reveals a good antistatic effect by forming a polyamide-ester consisting of aliphatic polyamide units and specified polyester units and obtain a resin composition having permanent antistatic properties by using the polymer. CONSTITUTION: This polyamide-ester is obtained by heating an aliphatic polyamide, a polyester and/or raw material therefor, a polyoxyalkylene glycol and an aromatic monohydroxy compound in the presence of a catalyst. It substantially consists of 10-80wt.% aliphatic polyamide units and 20-90wt.% polyester units containing both structural units of formula I (wherein R<1> is 1-12C hydrocarbon group; R<2> is 2-3C alkylene; and m is 30-140) in an amount of 5-50wt.% based on the polyamide-ester and at least one kind of structural units selected from among those of formula II (wherein R<3> is 2-12C alkylene), formula III (wherein R<4> is 2-12C alkylene and/or a 6-12C aromatic group) and formula IV (wherein R<5> is 2-12C alkylene).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel polyamide ester, a method for producing the same and a resin composition containing the same. More specifically, the present invention relates to a polyamide ester having a polyoxyalkylene glycol chain grafted onto a thermoplastic synthetic polymer, which is useful as a modifier capable of imparting excellent permanent antistatic property, a method for producing the same, and a control agent containing the same. The present invention relates to a resin composition having excellent electric performance.

[0002]

2. Description of the Related Art Thermoplastic synthetic polymers have excellent properties as materials and are widely used in various industrial fields. However, since thermoplastic synthetic polymers are generally hydrophobic, they are easily charged with static electricity. This is because, in addition to the appearance problem that dust tends to adhere when used in OA equipment and housing materials, when used in the field of electronics, which is rapidly advancing in recent years, static electricity of charged high voltage is generated in the circuit. It has become a major problem that affects the performance of the product, such as damage to the product or malfunction.

As a method for imparting an antistatic property to a thermoplastic synthetic polymer, many attempts have been made to introduce an ionic group into the thermoplastic synthetic polymer.

For example, a method of adding a surfactant containing a sulfonic acid group to a thermoplastic resin has been proposed (Japanese Patent Laid-Open No. 62-230835, Japanese Patent Laid-Open No. 5-222).
No. 241, JP-A-5-222357), the resin obtained by this method does not continue to have antistatic properties by treatment such as wiping or washing with water, and bleeding of the surfactant on the surface makes it unattractive. There is a problem.

Therefore, attempts have been made to use a polymer having an antistatic ability, which can fix the antistatic agent semipermanently, as the antistatic agent.

For example, it has been proposed to introduce a sulfonate into the molecular chain of polyamide or N-alkylated polyamide (USP-4006123, USP-
4035346). Although this polymer has excellent antistatic properties, it has a low Tg and low crystallinity, and therefore it is difficult to handle the polymer at a temperature of Tg or higher, for example, room temperature.
Not practical.

On the other hand, it is disclosed that a specific polyether ester amide is used as an antistatic agent for a thermoplastic resin (Japanese Patent Laid-Open No. 62-273252), but such a polyether ester amide is a polyoxyalkylene. It is a polymer in which glycol is introduced into the main chain by copolymerization. The polymer has a high antistatic ability, but in order to obtain sufficient antistatic performance, the copolymerization amount of such polyoxyalkylene glycol should be increased or it should be used in combination with a low molecular weight surfactant such as sodium dodecylbenzenesulfonate. It is necessary to enhance the effect by doing. However, when the copolymerization amount of such polyoxyalkylene glycol is increased, the mechanical properties and heat resistance of the polymer are lowered, and the degree of polymerization is difficult to increase. It has also been pointed out that when a low-molecular-weight surfactant is used in combination, when the molding time becomes long, the surfactant aggregates and remains inside the molding machine, or the surface and physical properties of the molded product are adversely affected. .

Therefore, under the present circumstances, it has not been possible to obtain a resin composition having excellent antistatic property by using a polymer having excellent antistatic property, mechanical properties and heat resistance alone.

On the other hand, JP-A-62-273252 discloses that a method of introducing polyoxyalkylene glycol as a copolymerization component into polyether ester amide can be carried out by melt polymerization reaction under high vacuum. There is. However, when a polymer grafted with polyoxyalkylene glycol is obtained, the polyoxyalkylene glycol has secondary carbon and thus has low polymerization reactivity. In such a polymerization reaction, the grafting rate is low and the degree of polymerization is increased. There are problems such as difficulty.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to provide an antistatic polymer exhibiting a good antistatic effect and a method for producing the same.

Another object of the present invention is to provide a resin composition having permanent electrification performance by mixing such an antistatic polymer with a thermoplastic resin.

[0012]

According to the present invention, the above-mentioned objects of the present invention are, first of all, aliphatic polyamide units 10-8.
In a polyamide ester consisting essentially of 0% by weight and 20 to 90% by weight of polyester unit, the polyester unit has the following formula (1)

[0013]

[Chemical 11]

[Wherein R 1 is a hydrocarbon group having 1 to 12 carbon atoms, R 2 is an alkylene group having 2 to 3 carbon atoms, and m is 30 to 1]
It is an integer of 40. ] And a structural unit represented by the following formulas (2) to (4)

[0015]

[Chemical 12]

[Here, R ³ is an alkylene group having 2 to 12 carbon atoms. ]

[0017]

[Chemical 13]

[Here, R ⁴ is an alkylene group having 2 to 12 carbon atoms and / or an aromatic group having 6 to 12 carbon atoms. ]

[0019]

Embedded image

[Here, R ⁵ is an alkylene group having 2 to 12 carbon atoms. ] A polyamide ester comprising at least one structural unit selected from the group consisting of

The polyamide ester of the present invention consists essentially of aliphatic polyamide units and polyester units,
The polyester unit has the following formula (1)

[0022]

[Chemical 15]

[Wherein R ¹ is a hydrocarbon group having 1 to 12 carbon atoms, R ² is an alkylene group having 2 to 3 carbon atoms, and m is 30 to
It is an integer of 140. ] The polyoxyalkylene glycol structural unit represented by these is contained.

In the above formula (1), R ¹ has 1 to ¹ carbon atoms.
12 hydrocarbon groups, preferably an alkyl group, a cycloalkyl group, an aryl group, or an alkylaryl group, and particularly preferably a C 1-6 alkyl group such as a methyl group or an ethyl group, or a phenyl group. An aryl group having 6 to 10 carbon atoms can be mentioned. R ² is an alkylene group having 2 to 3 carbon atoms, preferably an ethylene group. Also, R
² may be one type, but may include two or more types, for example, an ethylene group and a propylene group at the same time.

M is a positive integer indicating the degree of polymerization, and is 30 to
The range is 140. When the degree of polymerization is less than 30, the obtained polyamide ester does not exhibit the antistatic property, and the object of the present invention cannot be achieved. Further, when the degree of polymerization exceeds 140 and becomes large, the degree of polymerization of the obtained polyamide ester is difficult to increase, and the antistatic agent does not have sufficient physical properties. Particularly, when the polymerization degree is in the range of 40 to 100, particularly excellent antistatic property is exhibited.

The structural unit represented by the above formula (1) is preferably contained in the finally obtained polyamide ester in an amount of 5 to 50% by weight. If it is less than 5% by weight, the antistatic property of the polyamide ester may be insufficient, and 50% by weight
If it is more than the above range, the mechanical properties and handleability of the polymer may deteriorate. The content of such structural units is more preferably 10 to 10 in the finally obtained polyamide ester.
It is 40% by weight, more preferably 20 to 30% by weight.

On the other hand, the polyester unit constituting the polyamide ester of the present invention has the following formulas (2) to (4).

[0028]

Embedded image

[Here, R ³ is an alkylene group having 2 to 12 carbon atoms. ]

[0030]

[Chemical 17]

[Here, R ⁴ is an alkylene group having 2 to 12 carbon atoms and / or an aromatic group having 6 to 12 carbon atoms. ]

[0032]

Embedded image

[Here, R ⁵ is an alkylene group having 2 to 12 carbon atoms. ] At least one structural unit selected from the group consisting of

In the above formula (2), R ³ has 2 to 2 carbon atoms.
12 alkylene groups, which may be linear, branched, or cyclic.

As examples thereof, ethylene, trimethylene,
Tetramethylene, hexamethylene, octamethylene, decamethylene, dodecamethylene, neopentylene, 2,
Mention may be made of 4,4-trimethylhexamethylene, 1,4-cyclohexylene and methylene-cyclohexylene-methylene. Among these, alkylene groups having 2 to 6 carbon atoms such as ethylene, tetraethylene and hexamethylene are preferable.

R in the above equation (3)^Four Has 2 to 1 carbon atoms
The alkylene group of 2 is the above R ³ Same as
Can be Also, as an aromatic group having 6 to 12 carbon atoms
Are optionally substituted phenylene, naphthylene, etc.
Is mentioned. When substituted, the above formula (3)
Is the following formula (5)

[0037]

[Chemical 19]

[Here, Ar represents a trivalent aromatic group having 6 to 10 carbon atoms. M ⁺ represents an alkali metal ion, an alkaline earth metal ion, a phosphonium ion, or an ammonium ion. ] The sulfonic acid salt-containing dicarboxylic acid structural unit represented by

In the above formula (5), Ar has 6 to 6 carbon atoms.
It is a trivalent aromatic group of 10 and is preferably a benzene ring or a naphthalene ring, particularly preferably a benzene ring.

M ⁺ is an alkali metal ion such as Na ⁺ and K ⁺ , an alkaline earth metal ion such as Mg ²⁺ and Ca ²⁺ , a phosphonium ion or an ammonium ion.

Examples of the phosphonium ion include those represented by the following formula.

[0042]

Embedded image

In the formula, R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are the same or different and each is a C 1-18 alkyl group such as a methyl group, an ethyl group or a propyl group, a carbon group such as a phenyl group or a naphthyl group. It represents an aryl group of the formulas 6-18.

Examples of ammonium ions include those represented by the following formula.

[0045]

[Chemical 21]

In the formula, R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ are the same or different and each is an alkyl group having 1 to 18 carbon atoms such as a methyl group, an ethyl group and a propyl group, a carbon group such as a phenyl group or a naphthyl group. It represents an aryl group of the formulas 6-18.

Of these, M ⁺ is preferably an alkali metal ion or a phosphonium ion.

It is preferable that the sulfonic acid salt-containing dicarboxylic acid structural unit is contained in the polyamide ester in an amount of 0.5 to 15% by weight, since the antistatic property of the polyamide ester of the present invention is increased. . If the content is less than 0.5% by weight, the antistatic property of the polyamide ester may not be sufficient, and if it exceeds 15% by weight, the polymerization degree of the polyamide ester may be difficult to increase and the physical properties may deteriorate. The proportion of the structural unit contained in the polyamide ester is more preferably 1 to 10% by weight, further preferably 1.5 to 5% by weight.

In the above formula (4), R ⁵ has 2 to 2 carbon atoms.
12 alkylene groups. The alkylene group may be linear or branched, but is preferably linear.

Examples of the alkylene group include ethylene,
Examples thereof include trimethylene, tetramethylene, pentamethylene, hexamethylene and undecylene groups.
Of these, an alkylene group having 2 to 6 carbon atoms such as a pentamethylene group is preferable.

The polyester unit is composed of the structural unit represented by the above formula (1) and at least one selected from the structural units represented by the above formulas (2) to (4). ), (3) and (4) only are preferable because the polymerization degree of the polyamide ester is easily increased and the antistatic performance is more excellent. Further, the structural unit represented by the above formula (3) is more preferably a part or all of the structural unit represented by the above formula (5) from the viewpoint of antistatic performance.

The above polyester unit is phenol /
The reduced viscosity is 0.1 to 2.0 when measured at a concentration of 1.2 g / dl and a temperature of 35 ° C. in a 1,1,2,2-tetrachloroethane mixed solution (weight ratio 60/40). It is preferable. By using such a polyester, the obtained polyamide ester exhibits excellent antistatic properties and mechanical properties. The reduced viscosity is more preferably 0.2 to 1.5.
Is.

The above polyester unit can be synthesized by a conventionally known method using a dicarboxylic acid or its ester-forming compound and a (aliphatic) diol or its ester-forming compound for inducing it.

The aliphatic polyamide unit constituting the polyamide ester of the present invention includes the following formulas (6) and / or (7)

[0055]

[Chemical formula 22]

[0056]

[Chemical formula 23]

[In the formula (6), R ⁶ is an alkylene group having 4 to 12 carbon atoms. In the formula (7), R ⁷ has 4 to 12 carbon atoms.
Or an alkylene-arylene-alkylene group having 8 to 16 carbon atoms, and R ⁸ has 4 carbon atoms.
To 12 alkylene groups. ] The aliphatic polyamide which consists of a unit represented by these can be mentioned. In the above formula (6), R ⁶ is an alkylene group having 4 to 12 carbon atoms. The alkylene group may be linear or branched, but is preferably linear. Examples of such an alkylene group include tetramethylene, pentamethylene, hexamethylene, decamethylene, undecylene and the like. Of these, pentamethylene is preferred. When R ⁶ is pentamethylene, the above formula (6) is represented by the following formula (6) -a.

[0058]

[Chemical formula 24]

It is represented by A polymer composed of this unit is generally called nylon 6.

As the unit represented by the above formula (6), other than this, for example,

[0061]

[Chemical 25]

Mention may be made of:

In the above formula (7), R ⁷ is an alkylene group having 4 to 12 carbon atoms or an alkylene-arylene-alkylene group having 8 to 16 carbon atoms, and R ⁸ is an alkylene group having 4 to 12 carbon atoms. Is.

The alkylene group having 4 to 12 carbon atoms represented by R ⁷ and R ⁸ may be linear, branched, or cyclic.

Examples thereof include tetramethylene, hexamethylene, octamethylene, decamethylene, dodecamethylene, neopentylene, 2,4,4-trimethylhexamethylene and 1,4-cyclohexylene.

Of these, hexamethylene is preferred as R ^{7 and} tetramethylene is preferred as R ⁸ . In this case, the above formula (7) is the following formula (7) -a

[0067]

[Chemical formula 26]

It is represented by A polymer composed of this unit is generally called nylon 6,6.

Other units represented by the above formula (7) include, for example,

[0070]

[Chemical 27]

And the like.

Of these, the aliphatic polyamide unit is preferably a unit represented by the above formula (6) -a or (7) -a.

The above aliphatic polyamide unit can be produced by a conventionally known method using a lactam, a salt of a dicarboxylic acid and a diamine, or a dicarboxylic acid halide and a diamine component. In fact, it is more convenient and preferable to use commercially available polymer chips as they are,
This is one of the major features of the present invention.

The polyamide ester of the invention comprises 10 to 80% by weight of aliphatic polyamide units and 2 polyester units.
Substantially composed of 0 to 90% by weight. When the polyamide unit is less than 10% by weight, sufficient strength and heat resistance of the polyamide ester cannot be obtained, and when it exceeds 80% by weight, antistatic property is not exhibited. Preferably 20-70% by weight of aliphatic polyamide units and 30-% of polyester units.
80% by weight.

The polyamide ester of the present invention has a property that does not significantly change its properties, for example, 20% by weight or less of the whole,
The content of the polyester such as polyethylene terephthalate having an aromatic dicarboxylic acid such as terephthalic acid or isophthalic acid as a constituent is preferably 10% by weight or less.

The polyamide ester of the present invention is a phenol / tetrachloroethane mixed solvent (weight ratio 60/40).
Medium, the reduced viscosity measured at a concentration of 1.2 g / dl and a temperature of 35 ° C. must be 0.3 to 3.0. When it is less than 0.3, it causes deterioration of physical properties when mixed with other thermoplastic resin, and when it exceeds 3.0, it is difficult to mix and mold, which is not preferable. Reduced viscosity is preferably 0.4
~ 2.5.

The polyamide ester of the present invention described above is
When synthesized by the production method described below, it is synthesized as a polymer structure exhibiting effective properties as an antistatic agent, which is the object of the present invention, and is one of the features of the present invention.

That is, the aliphatic polyamide (a), the polyester and / or its raw material (b), and the following formula (8)

[0079]

[Chemical 28]

[Wherein R ⁹ is a hydrocarbon group having 1 to 12 carbon atoms, R ¹⁰ is an alkylene group having 2 to 3 carbon atoms, and n is 30 to
It is an integer of 140. ] The polyoxyalkylene glycol (c) represented by the above, and 5 to 100 parts by weight of the aromatic monohydroxy compound (d) per 100 parts by weight of the total weight of these (a), (b) and (c). The polyamide ester of the present invention can be produced by heating in the presence of a transesterification catalyst and then distilling off the aromatic monohydroxy compound.

As the aliphatic polyamide (a), those comprising the above-mentioned aliphatic polyamide unit can be used, and nylon 6, nylon 6 and 6 can be preferably used.

Such an aliphatic polyamide has an intrinsic viscosity of 0.1 as measured at a temperature of 35 ° C. using m-cresol as a solvent.
It is preferably from 5 to 3.0 in terms of antistatic property and heat resistance of the obtained polyamide ester, and 1.0 to 2.
A value of 0 is more preferable.

As the polyester and / or the raw material (b) thereof, a polyester comprising at least one structural unit selected from the group consisting of the above formulas (2) to (4), or a raw material of these polyesters can be used. .

Among them, the polyester is a polymer obtained by containing 0.5 to 15% by weight of the structural unit represented by the above formula (5) in the structural unit represented by the above formula (3). It is preferable because the antistatic performance of is improved.

The polyester was reduced in a phenol / 1,1,2,2-tetrachloroethane mixed solution (weight ratio 60/40) at a concentration of 1.2 g / dl at a temperature of 35 ° C. The viscosity is preferably 0.1 to 2.0. By using such polyester,
The obtained polyamide ester exhibits excellent antistatic properties and mechanical properties. The reduced viscosity is more preferably 0.2-1.
It is 5.

As the raw material of the polyester,
C2-C12 aliphatic dicarboxylic acid and / or ester-forming compound thereof, C6-C12 aromatic dicarboxylic acid and / or ester-forming compound thereof, C2-C12 aliphatic diol and / or The ester-forming compound, the C2-C12 cyclic ester compound, etc. can be used.

Examples of the aliphatic dicarboxylic acid or its ester-forming compound include adipic acid, sebacic acid, dimethyl adipate, dimethyl sebacate, diethyl adipate, diethyl sebacate, diphenyl adipate and the like. Among these, adipic acid, sebacic acid, dimethyl adipate, dimethyl sebacate and diphenyl adipate are preferable, and dimethyl adipate, dimethyl sebacate and diphenyl adipate are more preferable.

Examples of the aromatic dicarboxylic acid having 6 to 12 carbon atoms and / or its ester-forming compound include terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, dimethyl esters thereof, and the following formula (9).

[0089]

[Chemical 29]

[In the above formula (9), Ar ′ is the same as Ar in the above formula (5). R ^11, R ¹² is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, M ⁺ is the same as M ⁺ in the formula (5). ] A sulfonic acid salt-containing dicarboxylic acid represented by the above or an alkyl or aryl ester thereof can be used.

As a specific example, 5-sodium sulfo-
Isophthalic acid, alkali metal salt of sulfophthalic acid such as 2-potassium sulfo-terephthalic acid, 5-sodium sulfo-isophthalic acid dimethyl ester, alkali metal salt of dimethyl sulfophthalate such as 2-potassium sulfo-terephthalic acid dimethyl ester, 5-sodium Sulfo-isophthalic acid diethyl ester, 2-potassium sulfo-terephthalic acid diethyl ester, and other sulfophthalic acid diethyl ester alkali metal salts, 5-sulfoisophthalic acid tetrabutylphosphonium salt, 2-sulfoterephthalic acid tetrabutylphosphonium salt, and other sulfophthalic acid alkyl esters Sulfonates such as phosphonium salts, 5-sulfoisophthalic acid-tetrabutylphosphonium salt dimethyl ester, 2-sulfoterephthalic acid-tetrabutylphosphonium salt dimethyl ester Sulfophthalic acid diethyl ester alkylphosphonium salts, such as 5-sulfoisophthalic acid tetrabutylphosphonium salt diethyl ester and 2-sulfoterephthalic acid tetrabutylphosphonium salt diethyl ester, and alkylsulfonium acid alkylammonium salts and their esters , Sulfonaphthalenedicarboxylic acid alkali metal salts and esters thereof, and the like.

Of these, preferably, 5-sodium sulfo-isophthalic acid, 5-sodium sulfoisophthalic acid dimethyl ester, 5-sodium sulfoisophthalic acid diethyl ester, 5-sulfoisophthalic acid tetrabutylphosphonium salt, 5-sulfoisophthalic acid. -Tetrabutylphosphonium salt dimethyl ester, 5-sulfoisophthalic acid tetrabutylphosphonium salt diethyl ester.

Examples of the aliphatic diol or its ester-forming compound include ethylene glycol, propylene glycol and tetramethylene glycol. Of these, ethylene glycol and propylene glycol are preferable.

Examples of the cyclic ester compound having 2 to 12 carbon atoms include β-propiolactone, γ-butyrolactone and δ.
Examples thereof include valerolactone and ε-caprolactone. Of these, ε-caprolactone is particularly preferable.

The above-mentioned raw materials of polyester can be used alone or in combination of two or more kinds. Further, it may be used in combination with the above polyester.

The polyoxyalkylene glycol used in the present invention is a compound represented by the following formula (8).

[0097]

Embedded image

Here, R ⁹ and R ¹⁰ are the same as R ¹ and R ^{2 in} the above formula (1), respectively, and n is the same as m in the above formula (1).

Specific examples include polyoxyethylene glycol methyl 1,2-dihydroxypropyl ether, polyoxyethylene glycol phenyl 1,2.
-Dihydroxypropyl ether, polyoxyethylene glycol isopropyl 1,2-dihydroxypropyl ether, polyoxyethylene glycol n-butyl 1,2-dihydroxypropyl ether, polyoxyethylene glycol octylphenyl 1,2-dihydroxypropyl ether, polyoxyethylene Glycolnonylphenyl 1,2-dihydroxypropyl ether, polyoxyethylene glycol cetyl 1,2-
Polyoxyethylene glycol derivatives such as dihydroxypropyl ether, polyoxypropylene glycol methyl 1,2-dihydroxypropyl ether, polyoxypropylene glycol phenyl 1,2-dihydroxypropyl ether, polyoxypropylene glycol n-butyl 1,2-dihydroxy Polyoxypropylene glycol derivatives such as propyl ether, polyoxypropylene glycol octylphenyl 1,2-dihydroxypropyl ether, polyoxypropylene glycol ononylphenyl 1,2-dihydroxypropyl ether, polyoxytetramethylene glycol methyl 1,2- Dihydroxypropyl ether, polyoxyethylene glycol / polyoxypropylene glycol copolymer methyl 1, - can be exemplified dihydroxypropyl ether, polyoxyethylene glycol derivatives Among these, preferred. The above compounds may be used alone or in combination of two or more.

The amount of the above compound used is not particularly limited,
It is preferable to use it so that the polyamide ester finally obtained contains 5 to 50% by weight. If the amount used is less than 5% by weight, the antistatic property may be insufficient, and if it is more than 50% by weight, the mechanical properties and handleability of the polymer tend to be deteriorated. The amount of the above compound used is more preferably 10 to 10 in the finally obtained polyamide ester.
It is 40% by weight, more preferably 20 to 30% by weight.

According to the present invention, the above (a), (b) and (c) are heated together with the aromatic monohydroxy compound (d). As such an aromatic monohydroxy compound, a compound represented by the following formula (10) can be preferably used.

[0102]

[Chemical 31]

In the above formula (10), X is a methyl group,
It is an alkyl group having 1 to 3 carbon atoms such as an ethyl group, a halogen atom such as chlorine and bromine, and y is an integer of 0 to 3.

Examples of such aromatic monohydroxy compounds include phenol, m-cresol, p-cresol, o-cresol, 2,3-dimethylphenol,
2,4-dimethylphenol, 2,5-dimethylphenol, 2,6-dimethylphenol 3,4-dimethylphenol, 3,5-dimethylphenol, m-ethylphenol, o-ethylphenol, p-ethylphenol, m -Propylphenol, o-propylphenol, p-propylphenol, m-chlorophenol,
o-chlorophenol, p-chlorophenol, 2,4
-Dichlorophenol, 2,3-dichlorophenol,
2,5-dichlorophenol, 2,4,6-trichlorophenol and the like can be mentioned. Of these, phenol, p-chlorophenol, m-cresol, p-
Cresol is preferred.

The amount of the aromatic monohydroxy compound used is
It is 5 to 100 parts by weight based on 100 parts by weight of the total amount of (a), (b) and (c). If the amount used is less than 5 parts by weight, the reactions of (a), (b) and (c) (and (d)) do not proceed sufficiently. In such a case, problems such as deterioration of physical properties due to an increase in the degree of polymerization and heat deterioration due to a longer reaction time occur, which is not preferable.
If it is more than 100 parts by weight, it takes a long time to distill the aromatic monohydroxy compound from the polymerization system after the polymerization.
Not preferred. The amount of the aromatic monohydroxy compound used is preferably 10 to 50 parts by weight, more preferably 20 to 40 parts by weight, based on 100 parts by weight of the total amount of (a), (b) and (c).

The above (a), (b), (c) and (d)
The order in which they are allowed to exist in the reaction system is not particularly limited,
For example, a method of causing components (a) to (d) to simultaneously exist in the system and reacting by heating, a method of previously allowing components (b) and (c) to simultaneously exist in the system at the same time in advance, reacting by heating, and copolymerizing
Examples of the method include adding the components (a) and (d). In particular, the former is simple and can be used more preferably.

In heating, the above (a),
A catalyst is added to (b), (c) and (d). As the catalyst, a known transesterification catalyst is used. Preferred transesterification catalysts include, for example, alkali metal compounds, alkaline earth metal compounds, titanium,
Mention may be made of metal compounds such as tin, zinc, antimony, manganese, cobalt and germanium. The amount of the catalyst used is not particularly limited, but is preferably 0.0001 to 0.1% by weight, preferably 0.001 to 0.05% by weight, based on the produced polyamide ester.
Is more preferable.

The reaction temperature during the heating reaction is the above-mentioned (a),
It is preferable that (b), (c) and (d) are the temperatures at which they are melted or dissolved in the polymerization reaction system. Preferably, if the reaction temperature is 180 to 250 ° C and the reaction temperature is lower than 180 ° C, the polymerization does not proceed so much. On the other hand, if it is higher than 250 ° C, decomposition due to heat occurs, which is not preferable. A more preferable reaction temperature is in the range of 200 to 230 ° C.

The melting time is not particularly limited and is about 30 minutes to 8 hours, although it varies depending on the composition of the polymer finally obtained, the polymerization temperature and the like. It is preferably from 1 hour to 6 hours, more preferably from 2 hours to 5 hours.

As the final step of the method for efficiently producing the polyamide ester of the present invention, the aromatic monohydroxy compound needs to be distilled off from the polymerization system to be substantially removed. Examples of the method for removing the aromatic monohydroxy compound include a method in which the melting temperature is higher than the boiling point of the aromatic monohydroxy compound under the polymerization conditions. Gradually reducing the pressure of the reaction system in the latter half of the melting stage lowers the boiling point of the aromatic monohydroxy compound,
It is effective for distilling off this and can be preferably carried out.
By distilling off the aromatic monohydroxy compound, the polyoxyalkylene glycol-grafted polyamide ester of the present invention can be obtained.

Thus, it is preferable that the atmosphere during the polymerization is atmospheric pressure or increased pressure in an atmosphere of an inert gas such as nitrogen or argon in the initial stage of the reaction and gradually reduced in the latter stage of the reaction.

The polyamide ester of the present invention preferably has a common logarithmic value (LogR) of surface specific resistance R (Ω) of 11.0 measured at room temperature of 20 ° C. and relative humidity of 65%.
The following values are shown. If the surface resistivity is more than 11.0, when mixed with another thermoplastic resin, sufficient antistatic property may not be imparted. The surface resistivity is more preferably 10.0 or less.

According to the present invention, by mixing the above-mentioned polyamide ester with another thermoplastic resin in an amount of 1 to 50% by weight, excellent properties can be obtained without impairing the physical properties of the thermoplastic resin such as mechanical strength and heat resistance. It is also possible to provide a resin composition having permanent antistatic property.

That is, another object of the present invention is to provide a resin composition substantially composed of the above-mentioned polyamide ester and a thermoplastic resin component other than the above-mentioned polyamide ester, which is a component of the present invention. This is achieved by containing the polyamide ester in an amount of 1 to 50% by weight based on the resin composition.

As the thermoplastic resin component, the above-mentioned polyamide ester is used as an essential component, and as other components, polyester resin such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT), bisphenol A type (aromatic) Polystyrene resins such as polycarbonate resins, polyester carbonate resins, AS resins and ABS resins, polyamide resins, polyether resins, and polyether ester resins can be used alone or in combination of two or more.

The polyamide ester is contained in an amount of 1 to 50% by weight, preferably 2 to 40% by weight, more preferably 3 to 30% by weight, based on the entire resin composition. It exhibits excellent antistatic properties with a common logarithmic value (LogR) of the value (R) of 13.0 or less. When the content of the polyamide ester is less than 1% by weight of the whole, sufficient antistatic property is not exhibited, and when it exceeds 50% by weight, the physical properties inherent in the thermoplastic resin are deteriorated, which is not preferable.

The resin composition of the present invention can be produced by a conventionally known method using a melt extruder such as an extruder. At that time, it may be appropriately selected depending on the thermoplastic resin to be used, and the melt extrusion temperature or the melt extrusion speed at which the thermoplastic resin can be molded can be used.

Specific molding temperatures include, for example, polyethylene terephthalate resin at 270 to 300 ° C., polybutylene terephthalate resin at 230 to 260 ° C., polycarbonate resin at 260 to 290 ° C. and ABS resin. In case of 200 ~ 230 ℃
It can be preferably used in the range of.

Further, the resin composition of the present invention has excellent antistatic property due to the antistatic effect of the polyamide ester itself constituting the resin composition. Conventionally used surfactant type additives such as Na dodecylbenzene sulfonate, K dodecylbenzene sulfonate, Li dodecylbenzene sulfonate, etc. may be added to the composition.

In addition, various additives may be added if necessary. Examples of such additives include glass fiber, metal fiber, aramid fiber, ceramic fiber, potassium whisker, fibrous reinforcing agent such as carbon fiber, talc, calcium carbonate, mica, clay, titanium oxide, aluminum oxide, glass flake. , Various fillers such as milled fiber, metal flakes, metal powder, heat stabilizers represented by phosphoric acid esters and phosphorous acid esters, light stabilizers, lubricants, pigments, flame retardants, flame retardant aids Additives such as agents and plasticizers may be appropriately mixed.

[0121]

INDUSTRIAL APPLICABILITY The polyamide ester of the present invention is a polyamide ester having a polyoxyalkylene glycol-grafted structure in which a part of the diol residues constituting the polyamide ester is substituted with polyoxyalkylene glycol. This polyamide ester is superior in antistatic property to the conventional thermoplastics in which polyoxyalkylene glycol is incorporated in the main chain,
By mixing 50% by weight, it is possible to provide a resin composition having excellent physical properties with excellent permanent antistatic property. Furthermore, the properties of the polyamide ester can be further improved by containing the sulfonate-containing dicarboxylic acid structural unit.

Further, according to the present invention, a polyamide ester having a high concentration of polyoxyalkylene glycol grafted can be prepared by a simple method by directly using an aliphatic polyamide and using an aromatic monohydroxy compound as a reaction medium. Can be manufactured in. Such a polyamide ester is expected to have a block-like polyamide unit forming the main chain of the polymer, and is also excellent in heat resistance from this point.

[0123]

The present invention will be described in detail below with reference to examples, but the present invention is not limited to the examples. In the examples, "parts" means parts by weight.

(Viscosity measurement) The reduced viscosity of the obtained polyamide ester was 1.2 in a phenol / 1,1,2,2-tetrachloroethane mixed solution (weight ratio 60/40).
It was measured at g / dl and a temperature of 35 ° C.

The intrinsic viscosity of the polyamide was measured at a temperature of 35 ° C. using m-cresol as a solvent.

(Thermal characteristics) The melting point (Tm) of the polymer is D
The measurement was performed using SC under the conditions of a temperature rising rate and a temperature lowering rate of 10 ° C./min. The heat distortion temperature (HDT) of the resin composition molded product is 1/4 inch according to ASTM D648, and the load is 18.
It was measured at 6 kg / cm ² .

(Impact strength) The impact strength of a resin composition molded product containing a polyamide ester is ASTM D256.
According to 1/8 inch.

(Bending strength, flexural modulus) ASTM D7
90 was measured.

(Surface specific resistance) The surface solid resistance of the polyamide ester and the resin composition containing the polyamide ester was determined to be super insulation after being left in a constant temperature and humidity chamber at 20 ° C. and 60% relative humidity (HR) for 1 day. Total (SM manufactured by Toa Denpa Kogyo Co., Ltd.
-8210), and the applied voltage was 1000 V.

(Evaluation of Permanent Antistatic Property) Polyamide ester whose surface resistivity was previously measured and its molded product were soaked for 2 hours in a constant temperature shaking tank at 30 ° C. where tap water at a flow rate of 500 ml / min was constantly poured and washed with water. After that, water was wiped off and dried, and the surface resistivity was measured again in the same manner as described above.

[Example 1] Intrinsic viscosity 1.41 (terminal CO
49 parts of granular chips of nylon 6 (hereinafter abbreviated as Ny6) having an OH group amount of 66 equivalents / 10 ⁶ g and a terminal NH2 group amount of 15 equivalents / 10 ⁶ g) and ε-caprolactone (hereinafter abbreviated as CL)
70 parts (molar ratio Ny6 / CL = 30/70), 5.7 parts diphenyl adipate, 1,6-hexanediol 0.
3 parts, polyoxyethylene glycol methyl 1,2-dihydroxypropyl ether having a number average molecular weight of 2000, 34 parts (2.0 mol%), p-chlorophenol 50
Parts and 0.01 parts of tetrabutyl titanate were placed in a reaction vessel equipped with a stirrer and a vacuum distillation system, and heated to 250 ° C. in a nitrogen stream under normal pressure. After about 10 minutes, ε-caprolactone started ring-opening polymerization to become a cloudy solution, and after about 6 hours, became a homogeneous solution. During this time, the reaction solution gradually thickened. Next, the temperature was kept at 240 ° C., and the pressure was gradually reduced to a high vacuum state of about 20 mmHg after 10 minutes and 1 mmHg or less after 10 minutes, and the reaction was performed for 30 minutes under the same conditions.
During this period, p-chlorophenol was distilled from the polymerization system.

The obtained polymer had 21% by weight of an aliphatic polyamide unit and 3% of the structural unit represented by the above formula (1).
It is a polyamide ester containing 4% by weight. The polymer is a transparent polymer having a slight yellowish color in a molten state, and has a reduced viscosity of 1.68 and a DSC measurement result of Tm =
It was 202 ° C.

Chips obtained by crushing this polymer were placed on a M-50B molding machine manufactured by Meiki Seisakusho, at a cylinder temperature of 210 ° C.
The surface resistivity of the obtained molded product was measured under conditions of a mold temperature of 40 ° C., and the surface resistivity logR was 9.1 (Ω).

Comparative Example 1 Polyoxyethylene glycol methyl 1,2-dihydroxypropyl ether was replaced with polyethylene glycol 3 having a number average molecular weight of 2000.
Polymerization was performed in the same manner as in Example 1 except that 4 parts (2.0 mol) was used.

The polymer obtained was a yellowish-white cloudy polymer in the molten state and had a reduced viscosity of 1.1 and a DSC measurement result of T.
It was m = 201 ° C.

A molded product was prepared in the same manner as in Example 1, and the surface resistivity was measured. The surface resistivity logR was 9.
It was 8 (Ω).

[Example 2] Intrinsic viscosity 1.41 (terminal CO
49 parts of granular chips of Ny6 having an OH group amount of 66 equivalent / 10 ⁶ g and a terminal NH2 group amount of 15 equivalent / 10 ⁶ g) and CL7
0 part (molar ratio Ny6 / CL = 50/50), 2-sodium sulfo-isophthalic acid dimethyl ester 2 parts (0.
8 mol%), 13 parts (0.8 mol%) of polyoxyethylene glycol methyl 1,2-dihydroxypropyl ether having a number average molecular weight of 2000, 50 parts of p-chlorophenol, and 0.01 part of tetrabutyl titanate are stirred. And a reaction vessel equipped with a vacuum distillation system, and heated to 250 ° C. in a nitrogen stream under normal pressure. After about 10 minutes, ε-caprolactone started ring-opening polymerization to become a cloudy solution, and after about 6 hours, became a homogeneous solution. During this time, the reaction solution gradually thickened. Next, keep the temperature at 240 ° C and gradually reduce the pressure to 1
A high vacuum state of about 20 mmHg after 0 minutes and 1 mmHg or less after 10 minutes, and the reaction was performed for 30 minutes under the same conditions. During this period, p-chlorophenol was distilled from the polymerization system.

The polymer obtained had 43% by weight of aliphatic polyamide units and 12 units of the structural unit represented by the above formula (1).
It is a polyamide ester that contains 1.8% by weight of the structural unit represented by the formula (5). Such a polymer was a transparent polymer having a slight yellowish color in the molten state, and had a reduced viscosity of 1.0 and a DSC measurement result of Tm = 193.
° C.

Further, a molded product was prepared in the same manner as in Example 1 and the surface resistivity was measured.
The gR was 8.5 (Ω).

[Example 3] Of the total charged amount of 98 parts of Ny6 and ε-caprolactone, except that the constituent molar ratio of Ny6 and ε-caprolactone was changed to [Ny6 / CL = 30/70]. Polymerization was carried out in the same manner as in Example 2.

The polymer obtained is a clear, slightly yellowish polymer in the molten state, with a reduced viscosity of 1.0 and a DS of
From the C measurement result, Tm was 173 ° C.

Further, a molded product was prepared in the same manner as in Example 1 and the surface resistivity was measured.
R was 8.0 (Ω).

[Example 4] Of the total charged amount of 98 parts of Ny6 and ε-caprolactone, except that the molar ratio of Ny6 and ε-caprolactone was changed to [Ny6 / CL = 60/40]. Polymerization was carried out in the same manner as in Example 2.

The polymer obtained is a slightly yellowish transparent polymer in the melt and has a reduced viscosity of 1.1, a DS of
From the C measurement result, Tm = 205 ° C.

Further, a molded product was prepared in the same manner as in Example 1 and the surface resistivity was measured.
The gR was 8.9 (Ω).

Example 5 6 parts (2.4 mol%) of 5-sodium sulfo-isophthalic acid dimethyl ester and 39 parts (2.4 mol%) of polyoxyethylene glycol methyl 1,2-dihydroxypropyl ether were used. Polymerization was performed in the same manner as in Example 2 except for the above.

The polymer obtained is a slightly yellowish transparent polymer in the melt and has a reduced viscosity of 0.8, a DS of
From the C measurement result, Tm was 171 ° C.

Further, a molded product was prepared in the same manner as in Example 1 and the surface resistivity was measured.
The gR was 7.0 (Ω).

[Comparative Example 2] 5-Sulfo-isophthalic acid dimethyl ester, polyoxyethylene glycol methyl ester
Polymerization was carried out in the same manner as in Example 1 except that 1,2-dihydroxypropyl ether was not used.

The obtained polymer was a yellow and transparent polymer in a molten state, and had a reduced viscosity of 1.1 and a DSC measurement result of Tm = 200 ° C.

Further, a molded product was prepared in the same manner as in Example 1 and the surface resistivity was measured.
The gR was 13.1 (Ω).

[Examples 6 to 10, Comparative Example 3] Examples 1 to 1
5, and the polymer crushed chips obtained in Comparative Example 1 were mixed with polycarbonate resin chips ("Panlite" L-1250 manufactured by Teijin Chemicals), and then the cylinder temperature was 2
Molding was performed under the conditions of 60 ° C. and mold temperature of 40 ° C. The surface resistance and various physical properties of the obtained molded product were measured, and the results are shown in Table 1.

[Comparative Example 4] A polycarbonate resin chip ("Panlite" L-1250 manufactured by Teijin Chemicals Ltd.) was molded under the conditions of a cylinder temperature of 20 ° C and a mold temperature of 90 ° C. The surface resistance and various physical properties of the obtained molded product were measured, and the results are shown in Table 1.

Example 11 Chips obtained by pulverizing the polymer obtained in Example 5 were replaced with ABS resin chips (UT manufactured by Mitsui Toatsu Co., Ltd.).
After being mixed with -61), molding was performed under the conditions of a cylinder temperature of 230 ° C and a mold temperature of 40 ° C. The surface resistance and various physical properties of the obtained molded product were measured, and the results are shown in Table 1.

[Comparative Example 5] ABS resin chips (UT-61 manufactured by Mitsui Toatsu Co., Ltd.) were used at a cylinder temperature of 230 ° C and a mold temperature of 4
Molding was performed under the condition of 0 ° C. The surface resistance and various physical properties of the obtained molded product were measured, and the results are shown in Table 1.

Example 12 The polymer crushed chips obtained in Example 5 were mixed with AS resin chips (JSR AS-230 manufactured by Japan Synthetic Rubber Co., Ltd.), and then the cylinder temperature was 230 ° C. and the mold temperature was Molding was performed under the condition of 40 ° C. The surface resistance and various physical properties of the obtained molded product were measured, and the results are shown in Table 1.

[Comparative Example 6] An AS resin chip (JSR AS-230 manufactured by Japan Synthetic Rubber Co., Ltd.) was used at a cylinder temperature of 2
Molding was performed under the conditions of 30 ° C. and mold temperature of 40 ° C. The surface resistance and various physical properties of the obtained molded product were measured, and the results are shown in Table 1.

Example 13 Chips obtained by grinding the polymer obtained in Example 5 were mixed with polybutylene terephthalate resin chips (manufactured by Teijin Ltd., intrinsic viscosity 0.88), and then the cylinder temperature was 230 ° C. Molding was performed under the condition that the mold temperature was 40 ° C. The surface resistance and various physical properties of the obtained molded product were measured, and the results are shown in Table 1.

[Comparative Example 7] A polybutylene terephthalate resin chip (manufactured by Teijin Ltd., intrinsic viscosity 0.88) was molded under the conditions of a cylinder temperature of 230 ° C and a mold temperature of 40 ° C. The surface resistance and various physical properties of the obtained molded product were measured, and the results are shown in Table 1.

[Examples 14 and 15 and Comparative Examples 8 and 9] Chips obtained by crushing the polymer obtained in Examples 1 and 5, polycarbonate resin chips ("Panlite" L-1 manufactured by Teijin Chemicals Ltd.)
250), ABS resin chip (UT-61 manufactured by Mitsui Toatsu)
And sodium dodecylbenzene sulfonate were mixed at the weight ratio shown in Table 1, and the cylinder temperature was 230 ° C.
Molding was performed under the condition that the mold temperature was 40 ° C. The surface resistance and various physical properties of the obtained molded product were measured, and the results are shown in Table 1.

[0161]

[Table 1]

1) P1: Polyamide ester of Example 1 P2: Polyamide ester of Example 2 P3: Polyamide ester of Example 3 P4: Polyamide ester of Example 4 P5: Polyamide ester of Example 5 P6: Comparative Example 1 Polymer 2) DBS: sodium dodecylbenzene sulfonate

It can be seen that any of the resin compositions using the polyamide ester of the present invention effectively lowers the surface resistance without lowering the physical properties and has an excellent antistatic effect.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08G 69/42 NSN C08L 77/12 LQR 101/00 LTA

Claims (10)

[Claims] 1. An aliphatic polyamide unit of 10 to 80% by weight.
In a polyamide ester consisting essentially of 20 to 90% by weight of a polyester unit, the polyester unit is represented by the following formula (1): [Here, R ¹ is a hydrocarbon group having 1 to 12 carbon atoms, R ² is an alkylene group having 2 to 3 carbon atoms, and m is an integer of 30 to 140. ] And a structural unit represented by the following formulas (2) to (4): [Here, R ³ is an alkylene group having 2 to 12 carbon atoms. ] [Chemical 3] [Wherein R ⁴ is an alkylene group having 2 to 12 carbon atoms and /
Alternatively, it is an aromatic group having 6 to 12 carbon atoms. ] [Chemical 4] [Here, R ⁵ is an alkylene group having 2 to 12 carbon atoms. ] A polyamide ester containing at least one structural unit selected from the group consisting of: 2. The polyamide ester according to claim 1, wherein the structural unit represented by the formula (1) is contained in the polyamide ester in an amount of 5 to 50% by weight. 3. The structural unit represented by the above formula (3) has the following formula (5): [Here, Ar represents a trivalent aromatic group having 6 to 10 carbon atoms. M ⁺ represents an alkali metal ion, an alkaline earth metal ion, a phosphonium ion, or an ammonium ion. ] The structural unit represented by these is included, The polyamide ester of Claim 1 or 2 characterized by the above-mentioned. 4. The polyester unit has the above formula (1),
The polyamide ester according to claim 1, comprising the structural units represented by (3) and (4). 5. The aliphatic polyamide unit has the following formula (6):
And / or (7) [Chemical 7] [In the formula (6), R ⁶ is an alkylene group having 4 to 12 carbon atoms. In the formula (7), R ⁷ is an alkylene group having 4 to 12 carbon atoms or an alkylene-arylene-alkylene group having 8 to 16 carbon atoms, and R ⁸ is an alkylene group having 4 to 12 carbon atoms. ] It is a unit represented by these, The polyamide ester in any one of Claims 1-4 characterized by the above-mentioned. 6. An aliphatic polyamide (a), a polyester and / or a raw material thereof (b), and a compound represented by the following formula (8): [Here, R ⁹ is a hydrocarbon group having 1 to 12 carbon atoms, R ¹⁰ is an alkylene group having 2 to 3 carbon atoms, and n is an integer of 30 to 140. ] The polyoxyalkylene glycol (c) represented by the above, and 5 to 100 parts by weight of the aromatic monohydroxy compound (d) per 100 parts by weight of the total weight of these (a), (b) and (c). A method for producing a polyamide ester, which comprises heating in the presence of a transesterification catalyst and then distilling off the aromatic monohydroxy compound. 7. A polyester-forming component or a raw material for the polyester is represented by the following formula (9): [Here, Ar ′ is a trivalent aromatic group having 6 to 10 carbon atoms. R ¹¹ and R ¹² each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an aryl group having 6 to 10 carbon atoms. M ⁺ represents an alkali metal ion, an alkaline earth metal ion, a phosphonium ion, or an ammonium ion. ] The compound represented by these is used, The manufacturing method of the polyamide ester of Claim 6 characterized by the above-mentioned. 8. The aromatic monohydroxy compound is represented by the following formula (10): [Here, X is an alkyl group having 1 to 3 carbon atoms or a halogen atom, and y is an integer of 0 to 3. ] The compound represented by these, The manufacturing method of the polyamide ester of Claim 6 characterized by the above-mentioned. 9. A resin composition substantially composed of the polyamide ester according to claim 1 and a thermoplastic resin component other than the polyamide ester, wherein the polyamide ester is contained in the resin composition in an amount of 1 to 50% by weight. A resin composition comprising: 10. The thermoplastic resin component contains one or more selected from the group consisting of polyester resin, polycarbonate resin, polyester carbonate resin, polystyrene resin, polyamide resin, polyether resin and polyether ester resin. The resin composition according to claim 9, wherein